Manufacture of colored lacquers and film-forming coatings



Patented Jan. 25', 1938 I OFFICE.

MANUFACTURE or 'oonoaanmoouaas mar-roams. cosmos Achille Conaetti, aim, Switzerland, minorto arm of J. Gelgy A. G., Basel, Switzerland No Drawing. Application ombu- 2a, 1935, s

rial .No. 48,444 In Germany 'February 1,

This invention is an improvement in or a modification of that described in the specification ofthe U. S. patent application No. 702,097, filed December 12, 1933. I

The process of that specification consists in a production of colored lacquers and film-forming coating compositions, wherein a leuco-compound or finished dye'stuff of the triarylmethane-series containing a group or groups capable of combining with mordants is dissolved in a lacquer to be colored and is developed by means of chromic acid or a salt thereof to the colored chromium-compound. 1

In the specification of my U. S. patent application, Ser. No. 42,136, flled on 25th day of September 1935, this reaction is extended to 'other metals for producing colored lacquers containing metal-dyestufi-complexes.

The present invention is based on the observation that the process'is applicable also to.v azodyestufis which contain one or more groups capable of combining with a mordant and therefore being ableof forming complex metal salts. It is known that azo-dystuffs can be converted into the metal complexes of the dyestuff particularly in aqueous solution, by treatment with agents furnishing the metal-complex-component. The reaction, however,-difiers from case to case. It is common to all the processesto make the metal dyestufl-complex as a first operation and then to isolate it, which'is mostly dimcult or costly.

l In contrast, it is very. surprising that in the present invention the metal complex of the mordant-dyeing azo-dyestuff is} developed in the lacquer itself, namely by dissolving a suitable dye stufi in the lacquer and converting it into the metal complex in the finished lacquer by gently warming. For the process bothazo-dyestufls with groups capable of beingmordanted are suitable, whether soluble or insoluble in water.

The water-soluble dyestufis may be applied in the form 'of their free dyestufi acid or of a salt. The use of a soluble dyestufi or an insoluble dyestuff depends largely on the composition of the lacquer. If the original lacquer has not been made on the base of lower alcohols, but, as in,- the modern industry, with higher alcohols, esters or softening agents, it may happen that various acid azo-dyestufis, both in the form of the dyestuffacid or of a salt, are sparing1y.soluble in the lacquer to be colored. In these cases it is recommended to avoid the presence of one or more sulpho-groups in the dyestufl molecule which lend solubility in water. These water-insoluble dyestuffs are almost without exception freely soluble in all usual lacquer mixtures, such as a nitro-oellulose and acetyl-cellulose lacquers, and yield after development of the metal complex a completely clear colored lacquer ready for use.

In Example 4 of British specification No. 241,214

As lacquers may be lacquers and varnishes as they are listed in specification of U. S. patent application Ser.- No.

zlblaims. (CI.1%4 79 there is described a process for coloring caoutchouc by precipitating in an aqueous emulsion of the caoutchouc a dyestufl as a lake in the form of its metal compound. However, in that example 'a true insoluble dyestufi-metal-salt (pigment) in which the metal isbound as an ion is involved;

this is fundamentally different fromthe dyestuif metal-complexes with complex bound. metal of the present process. Furthermore, chlorinated rubber, for instance, is so different from caoutchouc in its properties that a process for coloring caoutchouc could not be transferred. without fundamental changes to the production of transparent colored lacquers on the base of chlorinated;

rubber.

It is advantageous to conduct the process in such a manner that the azo-dyestuff being able adapted for each individual case. The-quantity of agent furnishing the metal-complex-com ponent necessary for the formation of the lacquer depends on the constitution of the dyestuff used and must be ascertained by a preliminary test. In some cases it suffices to dissolve -the components in the lacquer to be colored at the temperature of the room. In most cases, however, it

is advisable to support dissolution and lacquer formation by gently warming.

Metals useful for the invention are all those which are used in the dye technics for theformation of complex dyestuif metal salts, particularly chromium, in the form of chromic acid or its salts; also copper, nickel, cobalt, iron, each in the form of a salt. It may be mentioned that these small quantities of metal salts are without influence on the properties of the finished coating compositions. The salts of the metals applied may be mixed as desired; it is also possible to mix with each other, without limit, the finished different fluid lacquers developed with various metal salts. I

used most film-forming As dyestufl's may be used, among those that are water-soluble, all those which are applicable inthe industry of producing mordant dyeings. In the following examples some members of this group are described.

or the dyestuffs insoluble in water there are -a,1oe,o1o. 3

2 Initial lacquer 1 Metal S8"! or acid Tint 22 52;?

38 0.4 Nitrocellulose lacquer" 0.2 Orange-yellow-.- Good. 39 0. 4 Acetyl-oellulose lacquer. 0. 2 Reddish-yellow Do. 40 0.4 do 0.2 Red-brown Do. 41 0.4 do 0. 2 Ferro-sulp ate sodi- Dark-brown Do.

, urn acetate.

42 0.4 Nitro-oelluloselacquer... 0.2 Nickel acetate Orange-yellow... Do.

- 43 0.4 do 0.2 Cobaltacetate Red Do. 44 0. 4 0. 2 Ferro-sulphate+sod1um Olive-brown Do.

acetate.

45 0.4 0.2 Copperacetate 0range-ycllow Do. 46 1 do 0.5 NazCnoq or Cl'Oa. Yellowish-red Do. 47 1 Acetyl-oelluloselacquen 0.5 do 48 i Nitro-celluloselacquer. 0.5 do D 49 2 Gelatine solution (with 1 addition quiantity of acetic oi a small a Chloro-caoutchouc lacquer.

51 0.5 Resin-spir1t-lacquer 0.25

- 52 0.5 Artiflcialresinlacquer... 0.25

53 1 Nitro-celluloselncquer- 0.5 54 1 Acetylcellulose lacquer. 0.5 55 2 Resin-spiritlacquer l 56 0.6 Nitro-celluloselacquer. 0.45 Deep-black 57 0.9 o 0.45 Yellowbrowrn. D0. 58 1.2 do Red-orange Do. 59 l. 2 Nickel-acetate Do.

Deep violet-brown What I claim is:

1. .A process for the manufacture of a colored composition comprising treating a hydrox'ymonoazodyestuff in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chlorocaoutchouc and gelatine with a compound of the group consisting of chromic acid, alkali bichromate, and acetates of Fe, Cu, Co and Ni.

2. A process for the manufacture of a colored composition comprising treating an orthohydroxymonoazodyestuff having an OH-group in ortho-position to the azo-group, in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chloro-caoutchouc and gelatine with a compound of the group consisting of chromic acid, alkali bichromate, and acetates of Fe, Cu, Co and Ni.

3. A process for the manufacture of a colored composition comprising treating a parahydroxymonoazodyestufi having an OH-group in para-position to the azo-group, in presence of a lac quer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chloro-caoutchouc and gelatinewith a compound of the group consisting of chromic acid, alkali bichromate, and acetates of Fe, Cu,

Co and Ni. r

4. A process for the manufacture of a col-- ored coniposition comprising treating an orthohydroxymonoazo-dyestufi of the general formula 5. A process for the manufacture, of a col-' ored composition comprising treating an orthohydr'oxymonoazo-dyestufi of the general formula R1N=NR1 orthrHOil wherein R1 represents the benzene radical of the diazo-component and R2 the'radical of a parasubstituted azo coupling component selected from the group consisting of benzene, naphthalene and quinoline radicals, in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chloro-caoutchouc and gelatine with a compound of the group consisting of chromic acid, alkali bichromate, and acetates of Fe, Cu, Co and Ni.

6. A process for the manufacture of a colored composition comprising treating a hydroxymonoazo-dyestuff of the general formula coon , wherein R1 represents the benzene radical of the diazo-component and R2 the radical of an azo coupling component selected from the group consisting of benzene and naphthalene radicals, in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial andnatural resins, chloro-caoutchouc and gelatine with a compound of the group consisting of chromic acid, alkali bichromate, and acetates of Fe, Cu, Co and Ni.

7. A process for the manufacture of a colored composition comprising. treating an orthohydroxymonoazo-dyestufi of the general formula whereinR represents the radical of an azo coupling component selected from the group consisting of benzene, naphthalene, quinoline, acetoacetic esters and pyrazolone radicals and X represents 'a member of the group consisting of halogen andnitro, in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins,

'ored composition comprising treating an orthohydroxymonoazo-dyestufi of the general formula fiNaN-R 5 1 X OH wherein R represents theradical of an azo coupling component selected from the group consisting of benzene, naphthalene, quinoline, aceto- .of the group consisting of chromic acid, alkali bichromate, and acetates of Fe, Cu, Co and Ni.

9. A process for the manufacture of a colored composition comprising treating a hydroxymonoazo-dyestufi inpresence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chlorocaoutchouc and gelatine with sodium bichromate.

10. A process for the manufacture of a colored composition comprising treating a hydroxymonoazo-dyestufi in presence of a lacquer constituent selected-from the group consisting of cellulose derivatives, artificial and natural resins, chlorocaoutchouc and gelatine with cobalt acetate.

11. A process for the manufacture of a colored composition comprising treating a hydroxymonoazo-dyestuil in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, i hi;loro-caoutchouc and gelatine with copper ace- 12. A process for the manufacture of a colored composition comprising treating an orthohydroxymonoazo-dyestufi made by coupling diazotized 4-nitro-amino-phenol with 1:3-dihydroxy-quinoline, in presence: of'a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chloro-caoutchouc and gelatine with a compound of the groupconsisting o f chromic'acid, alkali bichromate, and acetates of Fe, Cu, 00 and Ni.

13. A process for the manufacture of a colored composition comprising treating an orthohydroxymonoazo-dyestufi made by coupling diazotized ,3'-chloro-aniline with 2-hydroxy-benzoic acid, in presence'of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and'natural resins, chloro-caoutchouc and gelatine with a compound oi. the group consisting of chromic acid, alkali bichromate, and acetates of Fe, Cu, Co and Ni.

14. A process for the manufacture of a colored composition comprising treating an orthohydroxymonoazo-dyestufl' made by coupling diazotized 5'-nitro-2-amino-phenol with 1:3 diamino-benzene, in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chloro-caoutchouc and gelatine with a compound of the group consisting of chromic acid, alkali bichromate. and acetates of Fe, Cd, Co and Ni.

'15. A process for the manufactureof a colored composition comprising treating an orthohydroxymonoazo-dyestuif made by coupling -1iiazotized 4-nitro-aminophenol with 1:3-dihydroxy-quinoline, in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chloro-caoutchouc and gelatine with sodium bichromate.?

16. A process for the manufacture of a colored composition comprising treating an ortho-' hydroxymonoazo-dyestufl. made by coupling diazotized 3-chloro aniline with 2-hydroxy-benzoic acid, in presence of a lacquerconstituent selected from the group consisting of cellulose derivatives, artificial and natural resins, chlorocaoutchouc and gelatine with sodium bichromate.

17. A process for the manufacture of a colored composition comprising treating a monoazodyestufi made by coupling diazotized 5-nitro-2- amino-phenol -with 1:3-diamino-benzene, in presence of a lacquer constituent selected from the group consisting of cellulose derivatives, ar-

tificial and natural resin's, chloro-caoutchouc and gelatine with sodiumbichromate.

18. A process for the manufacture of a coloredcomposition comprising treating an orthohydroxymonoazo-dyestufi madeby coupling diazotized 4-nitro-aminophenol with 1:3-dihydroxy-quinoline, in presence of acetylcellulose with sodium bichromate.

19. A process for the manufacture of a colored composition comprising treating an orthohydroxymonoazo-dyestuif made by coupling diazotized 3-chloro-aniline with 2-hydroxybenzoicacid, in presence of acetylcellulose with, sodium bichromate. r.-

20. A process for the manufacture of a colored composition comprising treating a monoazodyestufi made by coupling diazotized 5-nitro-2- amino-phenol with 1:3-diamino-benzene, in presence of nitrocellulose with sodium bichromate.

21; The colored compositions comprising a lacquer constituent selected'from the group consisting of cellulose derivatives, artificial and natural resins, chloro-caoutchouc and gelatine, and a complexmetallic derivative of aihydroxymonoazo-dyestuif, the metal component being a member of the group consisting of Cr, Fe, Cu, Co and Ni, said compositions being soluble with intense, bright colorations in esters of organic acids and phenols used for the preparation of lacquers and mixtures thereof.

-- ACHILLE CONZE'I'II. 

